Antiwear gasoline composition and additives therefor



Feb. 1, 1966 SPARK PLUG LIFE (THOUSANDS OF MILES) F. T. FINNIGAN ETAL 3,232,724 ANTIWEAR GASOLINE COMPOSITION AND ADDITIVES THEREFOR Filed Nov. 17, 1961 SPARK PLUG SET MILEAGE TO REPLACEMENT g UNTREATED FUEL m] TREATED FUEL I53 I54 I63 I64 I65 I66 SQUAD NUMBERS INVENTORS PAUL E. PFEIFER BY FREDERICK 7T F/NNIGAN (Ea/WP A T TORNE Y United States Patent 3,232,724 ANTIWEAR GASOLINE COMPOSITION AND ADDITIVES TIEREFOR Frederick T. Finnigan and Paul E. Pfeifer, both of Crystal Lake, 111., assignors, by mesne assignments, to Union Oil Company of California, Los Angeles, Calif, a corporation of California Filed Nov. 17, 1961, Ser. No. 153,169 15 Claims. (Cl. 44-66) This invention relates to antiwear gasoline compositions containing a deposit-modifying agent, and a multipurpose additive serving as a detergent, de-icer, and surfactant. More particularly, this invention relates to leaded gasoline compositions containing dibutyl phthalate, mixed alkyl aryl phosphate esters, and a surfactant carburetor detergent, which meet the requirements for the operation of a modern, high-compression, internal-combustion engine as to performance rating, anti-knock qualities, fuel economy, spark-plug cleanliness, absence of inductionsystem deposits, and general increase in the power output of the engine. A particular feature of this invention is the finding that low concentrations of dibutyl phthalate, regardless of the presence of other additives, produce gasoline compositions which greatly reduce the wear of the parts of an internal combustion engine, particularly abrasive wear.

The dimensional changes of critical parts, such as bearings, cam lobes, cylinders, pistons, and piston rings, limit the useful lift of an internal-combustion engine. Engine life has been extended by improved metallurgy, new metal alloys, improved lubricating-oil compositions, thermostatic temperature control, crankcase ventilation, and more recently, fuel additives. With the advent of highcompression, high-rpm, high-torque engines, the dimensional clearances of the parts were greatly reduced, and the influence of dimensional changes on engine performance and engine life have been amplified, particularly wear caused by the abrasive action of dust particles in the engine.

Little is known regarding the influence of dust-particle sizes on wear, the effects of concentration of the dust particles, or the physical properties of the abrasive portions of the dust in relation to wear or wear rates. Early tests, wherein large quantities of a composite dust with a wide range of particle size were introduced into the induction system of a spark-fired engine for relatively long periods of time, showed the effect of the size of abrasive particles on piston ring and cylinder wear. In these tests, the dust comprised silica particles of about 50 to 20 microns in size, containing 5% of particles of 20-10 microns, 2.0% of particles of -5 microns, and 2.5% of particles of 50 microns. Using a standard 4- cycle engine, it has been reported that the presence of an air filter reduced piston top-land wear by 75%, pistonring wear by upwards of 80%, cylinder-bore wear by over 75%, valve-stem wear by about 50%, valve-guide wear by about 77%, main-bearing wear by about 80%, and crankshaft-journal wear by 30%, all of these values being approximations.

The use of both an air filter and an oil filter on an engine at the same time, according to previous investigations, further reduced the wear of these parts with the exception of the valve guides. The feed rate of the dust in these tests was high, being 0.236 g. per hundred cubic feet of air.

Corresponding tests with a single-cylinder diesel engine, using dust feed-rates of 0.033 g. per thousand cubic feet of air, well within normal operating conditions, also produced wear reductions, though not as pronounced, which were comparable to those from the internal-combustion engine tests.

"ice

C. E. Watson et al., in their more recent study entitled Abrasive Wear of Piston Rings, presented at the January 1955, annual SAE meeting, found that the amount of wear depends on the size and properties of the abrasive and the method by which the abrasive enters into the engine. These investigators further found that some abrasives cause only limited wear while others continue to cause wear as long as they are in the engine. This prolonged wear characteristic is related to the physical properties of the abrasive.

There is evidence that during the operation of an internal-combustion engine, the piston rings are separated from the cylinder walls by finite distances and this area of separation is apparently maintained by a hydrodynamic oil film. Certain of the dust particles appear to be carried by this oil film and thus are present to produce prolonged wear. One method of reducing this type of abrasive wear is to increase the efficiency and prolong the effectiveness of the air filter itself. Another method is to provide special formulations for the crankcase oil. Both of these methods result in improved piston-ring life.

A feature of this invention is the provision of a gasoline composition which, when used in conjunction with adequate air-cleaner facilities and adequately compounded crankcase oils, results in reduction of engine wear, particularly wear due to the abrasive action of dust particles taken into the intake system of the engine.

The use of upper-cylinder lubricants in gasolines is Well known. C. A. Bouman, Properties of Lubricating Oil and Engine Deposits, McMillian and Company, Limited, St. Martins St., London, England, defines an uppercylinder lubricant as an oil added to gasoline at concentrations from 0.25 to 0.5%. When an engine is stopped, the gasoline evaporates leaving an oil film which protects the wearing surfaces when the engine is next started. He points out the possible beneficial effect immediately after starting the engine, but also says that this effect is minor. He further points out that such materials, particularly at the higher concentrations, can lead to excessive engine deposits.

The additive treatment of gasolines described in this invention is distinct from conventional upper-cylinder lubricants in several respects, as follows.

(1) It is effective in concentrations considerably below the lower limit reported necessary for upper-cylinder lubricants.

(2) The antiwear effectiveness varies inversely with dibutyl phthalate concentration in the range from 12.5 lbs/1000 bbl. (0.005% wt.) to lbs/1000 bbl. (0.03% wt.)

(3) The additive treatment of this invention exhibits carry-over properties, i.e., reduced wear can be observed for some time after a change from treated to untreated gasoline.

(4) The instant additive treatment has a beneficial effect on engine deposits rather than the observed deleterious effects associated with upper-cylinder lubricants.

Accordingly, it becomes a primary object of this invention to provide a novel gasoline composition which reduces engine wear, particularly that occurring when an engine is subjected to abrasive dust.

Another object of this invention is to provide a novel gasoline composition which, in addition to reducing engine wear, meets all of the requirements necessary for a modern, high-compression, high-speed, internal-combustion engine.

An object of this invention is to provide treated gasoline compositions for modern internal-combustion engines which increase the economy and performance of the engine, prolong spark-plug life, reduce carburetor and induction system deposits, and reduce piston ring and cylinder wear to a minimum.

Another object of this invention is to provide a gasoline composition containing small amounts of dibutyl phthalate, which composition may include deposit modifiers, such as mixed alkyl aryl phosphate esters, and a surfactant carburetor detergent, such as alkylphenoxypolyethoxy alkanols.

These and other objects of the invention will be described or become apparent as the description thereof proceeds.

The drawing is a bar graph showing spark-plug mileage to replacement in 25,000-mile fleet tests using modern cars under stop-and-go service.

The gasoline compositions of this invention contain as the hydrocarbon portion thereof any of the known gasoline hydrocarbons boiling in the range of about 90 to 425 F., and preferably boiling in the range of about 90 to 400 F. The hydrocarbon portion of the gasoline may contain normal, branched-chain, and cyclic hydrocarbons having from 4 to 12 carbon atoms. The hydrocarbon portion of the gasoline also may contain products prepared in the chemical conversion of hydrocarbons to produce gasoline. Such conversion products include the products prepared by isomerization, alkylation, polymerization, cracking, disproportionation, hydrogenation, dehydrogenation, and combinations of such processes. A preferred gasoline composition contains a major proportion of the gasoline hydrocarbons prepared by fiuid catalytic cracking and a minor proportion of an alkylate prepared from isobutane and C and/or C olefins. More specifically, the base fuel may comprise about 80% of gasoline from the fluid catalytic-cracking process, and about 20% of the aforementioned alkylate, with or without the addition of about 2 to 4 ml. TEL/ gal. Other metal compounds and other lead alkyls, or combinations thereof, may be used in the compositions of this invention.

Based on a series of Wear tests, we have determined that, quite unexpectedly, dibutyl phthalate is a most effective antiwear agent, regardless of and without effect on the functions of other additives present, and it is particularly effective at low concentrations on the order of 6 to 25 lbs. per 1000 bbls. of gasoline in overcoming abrasive wear at the top of the cylinder bore and on the piston rings of the engine. It has also been found that dibutyl phthalate, when used at lbs. per 1000 bbls., is practically inefiective for this purpose, and the use of more than 25 lbs./ 1000 bbls. does not further enhance the wear inhibition. On a weight percent basis the concentration of dibutyl phthalate should be within the range of about 0.0024 to 0.01 wt. percent, and the most effective concentration is about 0.005 wt. percent, based on the hydrocarbon portion of the composition.

The alkyl aryl phosphate esters are from the group consisting of dimethyl phenyl phosphate, methyl diphenyl phosphate, and triphenyl phosphate. A preferred product comprises a mixture of dimethyl phenyl phosphate (45%), methyl diphenyl phosphate (15%), and triphenyl phosphate diluted with toluene to a phosphorus content of 11%.

About 0.2 to 0.45 and preferably about 0.3 theory of the alkyl aryl phosphate ester is used in the gasoline compositions of this invention.

The detergent portion of the gasoline composition of this invention, present in an amount ranging from about 0.001 to 0.01 weight percent based on the total composition, may be alkylphenoxypolyethoxy alkanols of the formula:

(00 11 nOAOH wherein R is an alkyl group of 8 or 9 carbon atoms, A is an alkylene group of 2 to 4 carbon atoms, and n is 4 to 16, but other surfactants which are sufiiciently (to about 0.001% Wt.) soluble in gasoline also may be used, e.g.,

aliphatic amine salts of carboxylic acids, such as the oleic acid salt of N-oleyl trimethylenediamine (Duomecn 0 Dioleate), and long-chain (16-22 carbon atoms) fatty acid salts of polyamines (RD 3134P); and long-chain aliphatic amides such as N-oleyl-N-;3-hydroxyethyl-ethylenediamine (MPA), one of a series of fatty amidomonoamines.

. The surfactant may be handled as a solution, e.g., 52% wt. MPA, 31% wt. isopropanol, 7% wt. xylene, and 10% wt. water, but all concentration figures given herein for dibutyl phtha-late are in terms of active ingredient.

EXAMPLE I The eifectiveness of various compounds as antiwear gasoline additives under abrasive wear conditions was studied using a single-cylinder COT engine. The compounds in this series of tests were selected because of some similarity to, or departure from, the physical or chemical characteristics of dibutyl phthalate, or of upper-cylinder lubricants of the prior art. The test results reported in. the following table are separated into two categories, the effective categorybeing those which caused a reduction in wear relative to the base fuel, and the no effect category being those which had no effect or caused an increase in wear relative to the base fuel. Each run included a test of the base fuel to provide a direct basis of comparison.

Table I.Abrasive-wear test results [COT screening tests] Run N0.

Wear rate, mgJhr.

Effective N 0 efiect 1 Base fuel Percent Base fuel reduction Additive Additive fuel fuel Dibutyl phthalate Triaryl phosphate Triaryl phosphate. Diphenyl phthalate Diphenyl phthalate Polybutene.

. Dibutyl carbitol Di-Z-ethylhexyl azelate- Dibutyl carbitol Castor oil #1 (a carooxytic ester) Polyalkylene glycol Polyalkylene glycol Dibutyl phthala-te Met-hylphenylpolysiln-wmp Methylphenylpoly ane Dibntyl phthalate Z Dibutyl phthalate 2 tJi t l acetate t-Butyl acetate ses me Table I .A brasiv-wear test results (Continued) [COT screening tests] Wear rate, mg./h.r.

Run No. Effective No effect 1 Base fuel Additive Percent Base fuel Additive fuel reduction fuel 21. Dibutyl terepnthalate 22. Dibutyl terephthalate 23. Extract #36 from High VI Bright Stock 4. O 2. 27

24. Extract %5 from High VI Bright Stock- 2. 57 1. 80

25. Extract #36 from High VI Bright Stock. 3. 29 2. 31

26. Extract #44 from Int. VI Neutral.

27. Extract #35 from Int. VI Bright Stock 1. 54 l.

28. Extract #35 from Int. VI Bright Stock- 2. 32 l. 78

29. Int. VI Bright Stock 3. 43 2. 26

30. Int. VI Bright Stock" 2. 87 2 24 31. Dibutyl phthalate 3. 4O 1 89 Additives showing zero, negative, or slightly positive antiwear effects.

Tl1e rings were replaced after Run 17. Run 18 is the first test after the new rings had been broken in.

Base fuel: 80% FCC, 20% alkylate, plus 3 ml. TEL/gal.

Additive dosage: 50 lb./1000 bbl. (as received, not necessarily 100% active ingredient).

As seen from the foregoing tests, piston-ring and topcylinder wear were reduced by certain additives, and aggravated by others, and dibutyl phthalate was the most effective antiwear agent.

EXAMPLE II The following description will demonstrate that dibutyl phthalate used in gasolines at concentrations from 12.5 to lbs/1000 bbl. performs a unique antiwear function in modern engines in a manner not related to conventional upper-cylinder lubricants.

The unique effectiveness of this additive was demonstrated by laboratory engine tests in a single-cylinder Cooperative Oil Test Engine (COT engine), and a 1958 Cadillac passenger-car engine. Two sets of test conditions were used for this work:

(1) Abrasive-wear tests in which the engine was operated under conditions of constant speed, load, and temperature with l-gram charges of dust introduced intermittently via the inlet manifold.

(2) Cyclic temperature tests in which the engine coolant temperature was cycled betwecn 60 F. and 210 F. every minutes.

This work, summarized below, shows the effectiveness of the subject additive treatment under these test conditions.

The cyclic temperature conditions force the ring and cylinder surfaces to continually re-orient themselves in response to the temperature changes, which in these tests occurred every half hour.

The laboratory wear tests were run by a matching technique in which each test involved a direct comparison between a base fuel and the base fuel treated with the additive being tested. The test was started with the engine running on the base fuel. When the base-fuel wear rate was established, usually 3-6 hours after starting the engine, the fuel supply was switched to the treated fuel without interrupting the engine run. The engine was then run for an equal period on the treated fuel. Test results were expressed as the percent reduction in wear for the Table II.A brasive-wear tests Lbs. DBP/1,000 bbl. Average percent wear reduction additive fuel compared with the base fuel. This direct comparison eliminated variables due to restarting the engine and day-to-day variations in basic engine conditions.

Table [IL-Cyclic-temperature tests Engine Lbs. DBP/1,000 bbl. Average percent wear reduction Includes .3 theory mixed alkaryl phosphate esters and 26 lb. alkylphenoxypolyethoxy alkanols/1,000 bbl.

2 Includes .3 theory mixed alkaryl phosphate esters and 12 lb. alkylphenoxypolyethoxy alkan01s/1,000 bbl.

Road tests were also carried out to evaluate the additive. A 1957 Oldsmobile equipped with a 12:1 compression ratio engine and equipment for radioactive ring-wear detection was used for this work. The car was driven over a 68-mile test course consisting of alternate sections of gravel and hard-surfaced roads. The data tabulated below represent the average of a number of repeated tests run over this course. The engine was equipped with a normally maintained oil-bath air cleaner. Base-fuel and additive-fuel were alternated to provide a direct comparison of wear rates.

Abrasive-wear road tests Lbs. DBP/ 1000 bbl. Percent wear reduction Both additive fuels also included .3 theory mixed alkaryl plsggpllfialte esters and 26 1b. alkylphenoxypolyethoxy alkanols/ It can be concluded that if DBP were acting as a simple upper-cylinder lubricant, its effectiveness would be expected to increase as the concentration was increased. In every case the opposite was true. As concentration was increased from 12.5 lbs/1000 bbl., the effectiveness was reduced. At less than 12.5 lbs/1000 bbl., there was not enough material to produce any effect, as indicated by the single test at 5 lbs/1000 bbl.

EXAMPLE 111 It was also observed that after an engine had been run on a treated fuel, wear was low for a considerable period of time before the base-fuel high wear rate was restored. We do not believe that a simple upper-cylinder lubricant would produce this effect. This carry-over effect is illustrated by the following data.

Extended tests equivalent to approximately 2500 miles of road operation were run in the COT engine under cyclic temperature conditions. Two tests were run on a gasoline without DBP. Two other tests were then run, alternating fuels, so that the equivalent of 200 miles of Fuel: Wear rate, mg./ 100 miles Base 7.5

Base 5.9 200 miles treated fuel/800 miles base fuel 4.5 200 miles treated fuel/ 800 miles base fuel 5.3

The reduced average wear for the runs in which the treated fuel was used occurred during both the ZOO-mile period on treated fuel and the BOO-mile periods on untreated fuel. Other examples of this carry-over effect have been observed in the engine test work.

EXAMPLE IV The final evaluation, however, came from the overall evaluation of fuels from all standpoints. A series of fleet tests was conducted to evaluate the gasoline compositions of this invention to compare miles per gallon, sparkplug performance, antiwear benefits, and carburetordetergency benefits obtained thereby. In making these toluene to a content of 11% phosphorus. A theory is defined as that amount of compound containing sufiicient phosphorus to completely react with the lead present to form lead phosphate, i.e., the amount of phosphorus necessary to completely react with the lead present to form lead phosphate.

A solution containing 52% Noleyl-N'-5-hydroxyethyl ethtylenediamine, 31% isopropanol, 7% xylene, and 10% W21 er.

The fleet tests were conducted using modern passenger cars in severe stop-and-go service. The results are shown as follows:

T able I V.F leet test-Gasoline utilization Car No. Fuel Test miles Average miles per gallo Untreated 24, 788 9. 6 Treated 24, 464 10. 8 do 24,890 10. 4 Untreated-.- 24, 364 8. 3 Treated--." 25, 960 10. 3 Untreated..- 25, 680 9. 6 Treated".-. 11. 4 ll. 3

tests, the untreated fuel had the following composition: 2* Pafflifill and flaphthfifle 61 Percent Table IV shows that the cars operating on untreated Olefins 16 Percent fuel during the 25,00O-rr1ile test period averaged 9.7 miles Aromatlcs 23 F per gallon, while the cars operating on treated fuel av- Tetfaethyllead 31111/ g eraged 10.7 mpg. This represents a 10% increase in Illustrating the invention, two treated fuels were used Iml s p r gallon. in the fleet tests. Approximately three-fourths of the ars 1 3 an 134 were 1958 mOdelS; Cars 167, 169 total miles on each car accumulated were with Treated and 170 were 1959 models; and cars 163, 164, 165 and Fuel No. l, and one-fourth with Treated Fuel No. 2. 166 were 1960 models. The cars were of two makes, The compositions of the two treated gasolines were as all with V-S engines. All of the cars were operated with follows: 33 the same high-detergency lubricating oil, SAE 20W. All

of the test engines were equipped with crankcase-ventila- Component F1101 No. 1 FuelNo. 2 tor dvices which fed crankcase fumes back into the intake manifold below the carburetor, and all were equipped g gg y phosphate theory theorywith either oil-bath or dry-element (paper) air cleaners, Dibntyl plithalate 12510571000 bbl. 12.5 lbs/1,000 0111. l filters- All Of the vehicles were Operated gi g g 'ggggfgggyb lbs/1709013) prlmarily in dense city traflic, in the same geographic lo- Isooctylphenoxytetraethoxy 20.01bs./1,000bb1. cation, and during winter, summer, and fall weather conethaml (Hem 305) ditions. At the completion of the tests the engines were disassembled for measurement and inspection. The fol- 1 Forty-five percent phenyl phosphate 40 7 trxphenyl phosphate, and 15% methyl diphenyl phospha e in solution in lowing Wear data Was accumulated- Table V.-Fleet test-Wear data from individual engines Top ring 2nd ring Cyl. bore wear in ring area, in.

Intake valve No. Fuel tulip de- Wt. loss, Gap ll'lG., in. Wt. loss, Gap mo, 1n. Top Center Bottom posit, gins.

gms. ms.

153 Untreated 1835 009 0507 000 0005 0002 0001 2. 0000 2151 013 0893 009 0000 0000 0005 5. 2040 1377 000 0305 003 0001 0000 0003 1. 0050 164 Untreated Avg 6183 02s 2638 014 0003 0004 0003 2. 2295 0910 044 4203 021 0012 0003 0000 3. 3770 4529 021 1932 010 0004 0001 0002 1. 3400 9 In summary, the above data shows that the average top-piston-ring weight loss for the four engines which operated on untreated fuel was 0.8379 gin, while the average for the four engines which operated on the Average cylinder-wall wear at the top of ring travel was:

Inch Untreated fuel 0.0008 Treated fuel 0.0004

Average cylinder-Wall wear in the center of ring travel was:

Inch Untreated fuel 0.0004 Treated fuel 0.0002

Average cylinder-wall wear at the bottom of ring travel was:

Inch Untreated fuel 0.0003 Treated fuel 0.0002

Average intake-valve-tulip deposit was:

Grams Untreated fuel 2.0253 Treated fuel 2.8506

This shows that the engine wear, on an average, was reduced by the following values in the engines operating on the treated fuel of this invention:

Percent reduction Top-ring weight loss 58 Top-ring gap increase 57 Second-ring weight loss 65 Second-ring gap increase 50 Cylinder bore:

Top-of-ring travel 50 Middle-of-ring travel 50 Bottom-of-ring travel 33 A separate determination of spark-plug life was made.

Spark-plug changes were made when misfire caused loss of engine performance. All changes were made as complete sets of plugs and there was no eifort to clean or regap spark-plugs. The results are shown graphically in the drawing. The spark-plug life averaged 6,740 miles with untreated fuel and 11,328 miles with treated fuel.

The spark-plug life was increased an average of 68%, on.

10 an overall basis, using the gasoline compositions of this invention.

Carburetor-cleanliness observations showed that in each instance the deposit level was significantly reduced with the treated fuel, particularly in the throttle body.

These test-fleet results show the wear protect-ion afforded the piston rings and cylinder bores through the use of the gasoline compositions of .this invention. Wear on these surfaces can cause reduction of compression pressures and increased oil consumption, with resultant loss in power and performance. Although the fleet-test results show that the gasoline compositions of .this invention reduce wear on these surfaces, it is logical to recognize that some wear will always occur due to the boundary lubrication conditions. If, based on the data presented herein, it is assumed that 0.0002" wear in the bore normally results from piston travel or motion in 25,000 miles of operation (in excess of 50,000,000 strokes of the piston), the wear attributable to the fuel could be reduced by that quantity. This would result in an average of 0.0006" wear at the top of the ring travel attributable to the characteristics of combustion of the untreated fuel, and 0.0002 attributable to the treated fuel, a reduction in wear of over 66% instead of the 50% value aforementioned. At the center of the ring travel and below, wear attributable to the fuel or its combustion is practically eliminated with the treated gasoline compositions of this invention.

Piston-ring wear is reflected in both weight loss and gap increase, as measured in a ring standard. A ring is subjected to wear on its face, which is exposed to the cylinder wall, and on its sides, which seal against the piston lands. Weight loss reflects wear on all three of these surfaces, while gap increase is associated with face wear only. The wear data reported herein indicate that either protection was being obtained in both respects, or that side wear was not significant, since reductions were obtained in both weight loss and gap increase to about the same degree.

A feature of this invention is the provision of a novel additive composition consisting essentially of dibutyl phthalate, the aforesaid phosphate ester, and the aforesaid surfactant-type carburetor detergent in such proportions that the herein described motor fuel compositions are obtained when sufficient-of the additive composition is added to leaded gasoline to provide from about 6 to about 25 pounds of dibutyl phthalate per 1000 barrels of gasoline. Specific examples of additive compositions useful for addition to gasolines in accordance with this invention are:

Forty-five percent dimethyl phenyl phosphate, 40% triphenyl phosphate, and 15% methyl diphenyl phosphate in solution in toluene to a content of 11% phosphorus. A theory is defined as that amount of compound containing sutficient phosphorus to completely react with the lead present to-form lead phosphate, i.e., the amount of phosphorus necessary to completely react with the lead present 'to form lead phosphate.

A solution containing 52% Noleyl-N'-fl-hydroxyethy1 ethylenediamine, 31% lsopropanol, 7% xylene, and 10% water.

Table VII gives the properties of representative gasolines that may be used with the additive composition of this invention.

Table VII .-Prpertzes of represen tatzve gasolmes Reid ASTM distillation (percent evaporated basis and corrected to 760 mmJHg Gasol ne Gravvapor TEL, descripity, presmlJgal.

tron API sure IBP E.P. Rec. Res. Loss 122/11 :1

01. 1 13. 2 83 93 112 145 179 203 224 242 260 288 327 369 94. 5 1. 2 4. 3 122. 7 2. 14 64. 9 12. 1 85 96 110 127 146 165 189 215 244 280 324 259 409 96. 5 1. 2 2. 3 119. 5 2. 58 64. 5 12. 7 S6 98 108 124 142 163 186 211 235 260 300 330 381 97. 2 1. 1 1. 7 116. 5 2. 60 67. 3 l2. 3 91 102 114 131 150 170 190 212 241 276 309 340 376 97. 2 1. 1 1. 7 119. 8 2. 03 57. 0 11. 3 91 122 152 179 205 228 242 258 274 297 314 365 96. 5 1. 1 2. 4 132. 2 2. 73 61. 0 10. B 89 101 112 132 156 180 211 237 264 296 334 355 375 97. 1 1. 3 1. 6 128. 4 2. 19 57. 3 11. 2 86 100 111 134 162 188 215 242 263 285 314 334 386 98. 7 1. 2 0. 1 127. 4 2. 78 61. 2 12. 2 96 99 156 184 211 235 260 288 320 399 95. 0 1. 0 4. 0 123. 0 2. 63 62. 8 12. 2 91 102 116 133 180 207 238 270 308 360 390 440 97. 8 1. 1 1. 1 123. 6 1. 60 58. 4 12. 4 96 105 116 138 166 195 226 258 286 314 349 376 406 96. 9 1. 1 2. 0 126. 0 2. 76 63. 6 12. 2 85 97 106 124 144 168 197 227 260 303 355 384 406 96. 9 1. 3 1. 8 119. 8 2. 31 60. 9 12. 9 91 97 112 136 164 191 215 240 270 307 364 437 95. 0 1. 1 3. 9 121. 8 1. 70 62. 1 11. 9 95 106 116 136 186 214 238 260 292 343 383 424 97. 8 1. 3 0. 9 125. 7 2. 33 63. 0 11. 4 82 102 114 134 158 186 215 238 258 285 337 376 416 97. 9 1. 3 0. 8 127. 0 2. 64 60. 9 10. 2 87 102 112 130 151 17 209 248 284 316 350 390 419 99. 0 0. 6 0. 4 129. 8 2. 70 60. 5 10. 8 89 107 128 153 172 196 220 244 279 300 340 366 408 96. 0 1. 0 3. 0 134. 0 1. 22 61. 8 11. 1 89 109 119 133 153 175 199 225 252 280 310 338 397 99. 0 0. 8 0. 2 126. 7 2. 72 57. 5 9. 8 92 110 118 132 146 168 199 230 250 272 302 321 394 99. O 0. 6 0. 4 135. 5 2. 90 61. 7 9. 5 91 110 121 139 157 176 200 228 256 296 334 356 382 98. 0 0. 9 1. 1 133. 4 2. 26 54. 7 11. 2 93 107 122 152 176 201 227 246 264 285 311 335 382 97. 0 0. 9 2. 1 132. 5 2. 99 61. 4 9. 5 93 108 120 138 158 180 204 229 252 278 315 344 382 98. 0 0. 8 1. 2 133. 6 1. 18 57. 9 9. 5 93 115 125 145 166 189 213 236 259 284 314 342 394 98. 7 1. 1 0. 2 136. 4 2. 62 66. 7 7. 9 99 125 138 159 181 208 228 245 260 281 314 346 383 98. 5 1. 4 0. 1 149. 3 2. 89 57. 7 9. 9 95 109 124 151 178 200 220 2 3 270 322 373 399 427 96. 0 1. 1 2. 9 136. 8 0. 98 59. 6 10. 1 95 108 121 141 166 191 216 240 266 296 332 362 410 97. 0 1.. 1 1. 9 133. 5 2. 05 64. B 10. 1 90 108 119 138 162 187 214 234 254 284 318 340 382 98. 0 1. 2 0. 8 132. 7 2. 78

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A motor-fuel composition consisting essentially of hydrocarbons boiling in the gasoline boiling range, about 6 to 25 pounds as substantially the only wear inhibitor of dibutyl phthalate per 1000 barrels of gasoline, about 2 to 4 milliliter of tetraalkyl lead per gallon of gasoline, about 0.2 to 0.45 theory of a phosphate ester of the group consisting of alkyl aryl phosphates, aryl phosphates and mixtures thereof, about 0.001 to 0.01 weight percent of a surfactant carburetor detergent of the group consisting of an alkyiphenoxypolyethoxy alkanol of the formula (O (EH4) HOAOH.

wherein R is an alkyl group of 8 to 9 carbon atoms, in is an integer of 4 to 16 and A is an alkylene group of 2 to 4 carbon atoms, the oleic acid salt of N-oleyl trimethylenediamine, fatty acid salts of polyarnines containing a total of 16 to 11 carbon atoms and N-oleyl-N-5-hydroxyethylethylenediamine.

2. A motor-fuel composition in accordance with claim 1 in which the concentration of said dibutyl phthalate is about 12 to 25 pounds per 1000 barrels of gasoline.

3. A motor-fuel composition in accordance with claim 1 in which said phosphate ester is present as a mixture comprising about 45 weight percent of dimethyl phenyl phosphate, about 40 weight percent of triphenyl phosphate and about 15 weight percent of methyl diphenyl phosphate.

4. A motor-fuel composition in accordance With claim 1 in which said surfactant carburetor detergent is isooctylphenoxytetraethoxy ethanol.

5. A motor-fuel composition consisting essentially of hydrocarbons boiling in the gasoline boiling range, about 3 milliliter of tetraethyl lead per gallon of gasoline about 0.3 theory of a mixture comprising about 45 weight percent of dimethyl phenyl phosphate, about 40 weight percent of triphenyl phosphate and about 15 weight percent of diphenyl phosphate, about 12.5 pounds of dibutyl phthalate as substantially the only wear inhibitor per 1000 barrels of gasoline and about 12 pounds of N-oleyl- N'-fl-hydroxyethyl-ethylenediamine per 1000 barrels of gasoline.

6. A motor-fuel composition consisting essentially of hydrocarbons boiling in the gasoline boiling range, about 3 milliliter of tetraethyl lead per gallon of gasoline, about 0.3 theory of a mixture comprising about 45 weight percent of dimethyl phenyl phosphate, about 40 Weight percent of triphenyl phosphate and about 15 weight percent of diphenyl phosphate, about 12.5 pounds of dibutyl phthalate as substantially the only wear inhibitor per 1000 barrels of gasoline and about 26.0 pounds of isooctylphenoxytetraethoxy ethanol per 1000 barrels of gasoline.

'7. A motor fuel additive composition consisting essentially of the following ingredients: (a) dibutyl phthalate, (b) a phosphate ester selected from the group consisting of alkyl aryl phosphates, aryl phosphates, and mixtures thereof, and (c) a surfactant carburetor detergent selected from the group consisting of an alkylphenoxypolyethoxy alkanol of the formula:

wherein R is an alkyl group of 8 to 9 carbon atoms, :1 is an integer from 4 to 16, and A is an alkylene group of 2 to 4 carbon atoms, the oleic acid salt of N-oleyl trimethylenediamine, fatty acid salts of polyamines containing a total of 16 to 22 carbon atoms, and N-oleyl-N fl-hydroxyethyl-ethylenediamine; said ingredients (a), (b) and (c) being present in such proportions that the motor fuel composition defined by claim 1 is obtained when said additive composition is added to a hydrocarbon motor fuel boiling in the gasoline range and containing from about 2 to about 4 milliliters of tetra alkyl lead per gallon, in an amount sufiicient to provide from about 6 to about 25 pounds of dibutyl phthalate per 1000 barrels of gasoline.

8. An additive composition in accordance with claim 7 in which said phosphate ester is present as a mixture comprising about 45 weight percent of dimethyl phenyl phosphate, about 40 weight percent of triphenyl phosphate and about 15 Weight percent of methyl diphenyl phosphate.

9. An additive composition in accordance with claim 7 in which said surfactant carburetor detergent is isooctylphenoxytetraethoxy ethanol.

10. A gasoline composition consisting essentially of hydrocarbons boiling in the gasoline boiling range containing from 2 to 4 milliliters of tetraethyl lead per gallon of gasoline and from 0.0024 to 0.01 weight percent of dibutyl phthalate as substantially the only wear inhibitor.

11. The method of operating an internal combustion hydrocarbons boiling in the gasoline boiling range containing from 2 to 4 milliliters of lead alkyl per gallon of gasoline and from 0.0024 to 0.01 weight percent of dibutyl phthalate.

13. A gasoline composition consisting essentially of hydrocarbons boiling in the gasoline boiling range containing as substantially the only wear inhibitor about 0.0024 to 0.01 Weight percent of dibutyl phthalate.

14. A gasoline composition in accordance with claim 13 containing about 0.001 to 0.01 Wt. percent of isooctylphenoxytetraethoxy ethanol.

15. A gasoline composition in accordance With claim 13 containing about 0.2 .to 0.45 theory of a phosphate ester of the group consisting of alkyl aryl phosphates, aryl phosphates and mixtures thereof.

References Cited by the Examiner UNITED STATES PATENTS Backofi et al 4470 X Caprio 4469 Colwell et al 44--77 Stayner et a1 4477 X Lindstrom et al 4466 Cosgrove et al 4472 Orlotf et a1. 4469 Segworth et a1. 4456 Hinkamp 4456 Australia.

DANIEL E. WYMAN, Primary Examiner. 

1. A MOTOR-FUEL COMPOSITION CONSISTING ESSENTIALLY OF HYDROCARBONS BOILING IN THE GASOLINE BOILING RANGE, ABOUT 6 TO 25 POUNDS AS SUBSTANTIALLY THE ONLY WEAR INHIBITOR OF DIBUTYL PHTHALATE PER 1000 BARRELS OF GASOLINE, ABOUT 2 TO 4 MILLILITER OF TETRAALKYL LEAD PER GALLON OF GASOLINE, ABOUT 0.2 TO 0.45 THEORY OF A PHOSPHATE ESTER OF THE GROUP CONSISTING OF ALKYL ARYL PHOSPHATES, ARYL PHOSPHATES AND MIXTURES THEREOF, ABOUT 0.00U TO 0.01 WEIGHT PERCENT OF A SURFACTANT CARBURETOR DETERGENT OF THE GROUP CONSISTING OF AN ALKYLPHENOXYPOLYETHOXY ALKANOL OF THE FORMULA 